Fibre-reactive formazane dyes containing β-sulfatoethylsulfonyl bonded via phenylaminotriazinylamino bridge members

ABSTRACT

The fibre-reactive formazan dyes of the formula ##STR1## in which R is C 1  -C 4  alkyl, C 1  -C 4  alkoxy, halogen, cyano or nitro, X is fluorine or chlorine, and n is the number 0, 1 or 2 produce dyeings which have good fastness properties on nitrogen-containing or hydroxyl-containing fibre materials.

The present invention relates to novel fibre-reactive formazan dyes,processes for their preparation and the use of these dyes for dyeing andprinting fibre materials.

The present invention relates to fibre-reactive formazan dyes of theformula ##STR2## in which R is C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen,cyano or nitro, X is fluorine or chlorine, and n is the number 0, 1 or2.

Examples of suitable C₁ -C₄ alkyl as R in the formula (1) are methyl,ethyl, propyl, isopropyl, butyl, tert-butyl, sec-butyl or isobutyl, inparticular methyl.

Examples of suitable C₁ -C₄ alkoxy as R in formula (1) are methoxy,ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, sec-butoxy orisobutoxy, in particular methoxy.

Examples of suitable halogens as R in formula (1) are fluorine, bromineor preferably chlorine.

Dyes of the formula (1) in which n is the number 0 are preferred.

Furthermore, dyes of the formula (1) in which X is chlorine arepreferred.

The invention furthermore relates to a process for the preparation ofthe dyes of the formula (1), which comprises reacting a compound of theformula ##STR3## in which R and n are as defined in formula (1) with acompound which introduces the radical of the formula ##STR4## in which Xis as defined in formula (1), or condensing a compound of the formula(2) first with a compound of the formula ##STR5## in which X is fluorineor chlorine and Hal is in each case halogen, in particular fluorine orchlorine, and then reacting the condensation product with a compoundwhich introduces the radical of the formula ##STR6##

Suitable compounds which introduce the radical of the formula (3) arepreferably the corresponding halides, in particular chlorides orfluorides. Examples are: ##STR7##

A preferred embodiment of the process according to the inventioncomprises condensing a compound of the formula (2) first with a compoundof the formula ##STR8## in which X is fluorine or chlorine and Hal is ineach case halogen, in particular fluorine or chlorine and then reactingthe condensation product with a compound which introduces the radical ofthe formula ##STR9##

Examples of suitable compounds of the formula (4) are cyanuric fluorideand cyanuric chloride. An example of suitable compounds which introducethe radical of the formula (5) is 4-(β-sulfatoethylsulfonyl)aniline.

The reaction of the compound of the formula (2) with the compoundintroducing the radical of the formula (3) or the condensation of thecompound of the formula (2) with the compound of the formula (4) and thesubsequent reaction of the condensation product with the compound of theformula (4) and the subsequent reaction of the condensation product withthe compound introducing the radical of the formula (5) is preferablycarried out in aqueous solution, emulsion or suspension, at lowtemperature, for example 0° to 40° C., and at a weakly acidic, neutralto weakly alkaline pH. Advantageously, the hydrogen halide liberated inthe condensation is continuously neutralized by adding aqueous alkalimetal hydroxides, alkali metal carbonates or alkali metal bicarbonates.

Preferably, compounds of the formula (2) in which n is the number 0 areused for the process according to the invention.

In a further preferred embodiment of the process according to theinvention, a compound introducing the radical of the formula (3) inwhich X is chlorine is used.

Preferably, cyanuric chloride is used as compound of the formula (4).

The compounds of the formula (2) are known per se or can be preparedanalogously to known compounds. Regarding the preparation of the coppercomplexes of the tetradentate formazans, see K. Venkataraman, TheChemistry of Synthetic Dyes, Volume VI, pages 287 to 297, Academic PressNew York and London (1972) and Ullmanns Encyklopadie der technischenChemie (Ullmanns Encyclopaedia of Industrial Chemistry), volume 11,pages 714 to 718, Verlag Chemie (1976).

The compounds which introduce the radical of the formula (3), or (5) andthe compounds of the formula (4) are also known per se or can beprepared analogously to known compounds.

The dyes of the formula (1) are suitable for dyeing and printing a widerange of fibre materials, in particular textile fibre materials,preferably hydroxyl- or nitrogen-containing textile materials, forexample silk, cellulose fibre materials and in particular wool,synthetic polyamide fibre materials, for example nylon-6 and nylon-6,6,and leather and paper. The dyes of the formula (1) give level dyeings inblue hues which have good general fastness properties, in particulargood wet fastness, for example wet rub fastness and good light fastness.Furthermore, the dyes of the formula (1) show very good properties whencombined with other reactive dyes. The abovementioned textile materialcan be present in a wide range of processing forms, for example as yarn,woven fabric or knitted fabric.

It should be mentioned in particular that the dyes of the formula (1)have high stability to reduction, good exhaustion properties and goodfixation speed and high fibre levelness and do not show dichroism.

The dyes according to the invention of the formula (1) which contain twosulfo groups are present either in the form of their free acid orpreferably as their salts. Examples of suitable salts are alkali metal,alkaline earth metal or ammonium salts or the salts of an organic amine.Examples are the sodium salts, lithium salts, potassium salts orammonium salts or the salt of triethanolamine.

Furthermore, the suitability of the dyes according to the invention ofthe formula (1) for the trichromic dyeing and printing of natural orsynthetic polyamide fibre materials together with a fibre-reactiveyellow or orange dye and a fibre-reactive red dye may be mentioned inparticular.

Trichromic dyeing is understood to mean the additive colour mixing ofsuitably chosen yellow or orange, red and blue dyes, by means of whichvirtually any desired hue on the visible colour spectrum can be obtainedby a suitable selection of the relative amounts.

The dyes to be used in the trichromic process should have uniform colourbuild-up in combination with constancy of shade in variousconcentrations and good combination behaviour.

Accordingly, the invention also relates to a process for the trichromicdyeing or printing of natural and synthetic polyamide fibre materials bymeans of dye mixtures of fibre-reactive dyes, wherein a blue dye of theformula (1) is used together with a yellow or orange sulfo-containingreactive dye and a red sulfo-containing reactive dye.

In particular, fibre-reactive sulfo-containing yellow or orange and redazo dyes are used which contain as fibre-reactive group preferably ahalogenotriazine or halogenopyrimidine group or a group of the aliphaticseries.

Preferably, the halogenopyrimidine group or group of the aliphaticseries which are used as fibre-reactive group is preferablydifluorochloropyrimidinyl, in particular2,4-difluoro-5-chloropyrimidinyl, or α,β-dihalogenopropionyl, inparticular α,β-dibromopropionyl, or α-halogenoacryloyl, in particularα-bromoacryloyl.

Examples of suitable yellow or orange sulfo-containing fibre-reactivedyes are as follows: ##STR10##

Examples of suitable red sulfo-containing fibre-reactive dyes are asfollows: ##STR11## in which acyl is, for example, acetyl or substitutedor unsubstituted benzoyl.

The fused rings indicated by dots represent naphthalene systems whichare possible as an alternative. ##STR12##

In the formulae above, R' is a fibre-reactive radical, in particular afibre-reactive radical of the halogenotriazine or the halogenopyrimidineseries or of the aliphatic series; preferably, R' isdifluorochloropyrimidinyl or α,β-dihalogenopropionyl orα-halogenoacryloyl. Particularly preferably, R' is2,4-difluoro-5-chloropyrimidin-6-yl or α,β-dibromopropionyl orα-bromoacryloyl.

In the process according to the invention for the trichromic dyeing orprinting of natural and synthetic polyamide fibre materials, theabovementioned dyes, in particular those of the formula (1) in which Xis chlorine or n is the number 0 and in particular those of the formula(1) in which n is the number 0 and X is chlorine are used as blue dyes.

Particularly preferred yellow or orange dyes are: ##STR13##

Particularly preferred red dyes are: ##STR14##

The invention also relates to trichromic dye mixtures, which contain ablue dye of the formula (1) together with a yellow or orangesulfo-containing reactive dye and a red sulfo-containing reactive dye,and in which the blue dye of the formula (1), the yellow or orangesulfo-containing reactive dye and the red sulfo-containing reactive dyehave the abovementioned meanings and preferences.

The yellow or orange and red dyes used in the process according to theinvention for the trichromic dyeing or printing and in the trichromicdye mixtures according to the invention are known or can be preparedanalogously to known dyes. The dyes are present either in the form oftheir free sulfonic acid or preferably as their salt, it being possibleto use the same salts mentioned for the dyes of the formula (1).

The amounts in which the dyes of the formula (1) and the yellow ororange and red fibre-reactive dyes can be used in the dye baths orprinting pastes can vary within wide limits, depending on the desiredcolour depth; in general, amounts of 0.01 to 10% by weight, inparticular 2 to 10 per cent by weight, relative to the material to bedyed or to the printing paste, have proved to be advantageous.

Preferably, natural polyamide fibre material, in particular wool, isused in the process according to the invention.

Special equipment is not required in the process according to theinvention. The customary dyeing and printing apparatuses and machines,for example for loose fibres, tops, yarn in hank form, wound packages,piece goods and carpets can be used.

In addition to the reactive dye, the aqueous dye baths can containdyeing assistants, in particular levelling assistants. The levellingassistants are used in an amount of 0.3 to 3 per cent by weight,relative to the fibre material.

As further dyeing assistants, the dye bath can contain mineral acids,such as sulfuric acid, sulfamic acid or phosphoric acid, organic acids,advantageously lower aliphatic carboxylic acids, such as formic acid,acetic acid or maleic acid. The acids serve in particular to adjust thepH of the liquors used according to the invention.

Preferably, the pH of 3 to 6 is adjusted by means of an organic acid, inparticular formic acid or acetic acid.

Preferably, the dyeing is carried out at a pH of 4 to 6, in particular4.2 to 5.5.

Furthermore, the dye liquor can contain various salts, in particularammonium salts or alkali metal salts, for example ammonium sulfate orsodium sulfate as dyeing assistants.

The liquor ratio can be chosen within a wide range, from 6:1 to 80:1,preferably 10:1 to 50:1.

The dyeing is carried out from aqueous liquor by the exhaust method, forexample, at a temperature between 80° and 105° C. or 110° C. if awool-protecting agent which eliminates formaldehyde is used, preferably98° and 103° C.

The dyeing time is usually 30 to 90 minutes.

In a particularly preferred embodiment of the process according to theinvention, the dye liquor is allowed to cool after the dyeing atpreferably 98° to 103° C. to about 75° to 90° C. and the pH is adjustedto 8 to 9, preferably to about 8.5. The pH can be adjusted withconventional agents, for example alkali metal hydroxide solutions and inparticular with aqueous ammonia solution of the usual concentration, forexample containing 25 per cent by weight of ammonia.

In the examples which follow, parts are by weight. The temperatures aredegrees centigrade. Parts by weight relate to parts by volume as thegram relates to cubic centimetres.

EXAMPLE 1

3.37 parts of 4-(2'-sulfatoethylsulfonyl)aniline are taken up in 50parts of water and dissolved at room temperature at a pH of 5 to 6 withsodium hydroxide solution. After the addition of 1.26 parts of sodiumacetate and cooling to 0° to 2°, a solution of 2.43 parts of cyanuricchloride in 20 parts of acetone is added dropwise over a period of 10 to15 minutes, while maintaining the pH at 6.25 with sodium hydroxidesolution. After the condensation is completed, the white product isfiltered off with suction and washed with a small amount of water. Thesolid product is suspended in 75 parts of 2-methoxyethanol and 25 partsof water and cooled to 10°. A solution of 5.96 parts of the chromophoreof the formula (101) ##STR15## in 50 parts of water is added dropwise tothis suspension over a period of 30 minutes, while maintaining the pH at6.5 with sodium hydroxide solution. After stirring overnight andaddition of sodium chloride, the dye is filtered off with suction andwashed with sodium chloride solution. Drying at 60° to 70° gives 10.1parts of a dye which has the formula (102). ##STR16##

The dye of the formula (102) dyes wool in blue hues which have goodfastness properties.

EXAMPLE 2

2.81 parts of 4-(2-sufatoethylsulfonyl)aniline are taken up in 42 partsof water and dissolved at room temperature at a pH of 6.5 by means ofsodium hydroxide solution. After cooling to 0° to 2° C., 11.49 parts ofcyanuric fluoride are added dropwise over a period of 1 to 2 minutes,while maintaining the pH at 6 to 6.5 by adding sodium hydroxidesolution. After the condensation is completed, a solution of 5.96 partsof the chromophore of the formula (101) in 50 parts of water is addeddropwise at 5° over a period of 10 minutes, while maintaining the pH at6.25 with sodium hydroxide solution. After stirring at room temperatureand addition of sodium chloride, the dye is filtered off with suction,washed with sodium chloride solution and dried at 60° to 70°. This gives5.0 parts of a dye which has the formula (103). ##STR17##

The dye of the formula (103) dyes wool in blue hues which have goodfastness properties.

DYEING EXAMPLE 1

4 parts of 80% acetic acid, 2 parts of the ammonium salt of themonosulfate of the adduct of a fatty amine (consisting of 30% ofhexadecylamine, 25% of octadecylamine and 45% of octadecenylamine and 7mol of ethylene oxide) and 4 parts of ammonium sulfate are dissolved insuccession in 4000 parts of water at 50°.

4 parts of the dye obtained according to Example 1 are dissolved in 100parts of hot water and added to the above dyebath. 100 parts ofprewetted tops of a wool knitting yarn are then placed into the dyebath,and the temperature of the bath is increased from 50° to 80° over aperiod of 30 minutes. After dyeing at 80° for 20 minutes, the bath isheated to boiling and the dyeing is then continued for 90 minutes at theboiling temperature. The dye shows almost complete exhaustion onto thesubstrate. After the bath has been cooled to 80°, the pH of about 4.5 israised to a permanent value of 8.5 by adding ammonia solution, and thedyed material is aftertreated at this temperature for 20 minutes. Afterthorough rinsing with hot and cold water, acidification with 1 part of80% formic acid, centrifugation and drying, a dark blue coloured woolyarn of very good wet and rub fastness and excellent light fastness isobtained.

DYEING EXAMPLE 2

A wool fabric which has been given an anti-felting finish is impregnatedwith a preparation described below and squeezed off on a pad-mangle to aliquor pickup of 250%.

    ______________________________________                                           4 parts of Diaprint REG ® (acid-resistant thickener),                    1 part of sulfamic acid                                                      0.2 part of thymol                                                            0.2 part of emulsifier                                                        94.6 parts of water                                                           100 parts                                                                    ______________________________________                                    

The impregnated material is then pressed in a heatable press at 100° to105° for 3 minutes under a pressure of about 0.5 kg/cm² together with atransfer paper which carries a printing pattern applied in the usualmanner by means of the dye according to Example 2. After rinsing anddrying, the wool fabric has the corresponding blue printing patternwhich has very good fastness properties.

DYEING EXAMPLE 3

A flannel fabric consisting of chlorinated wool is impregnated on apad-mangle with the dye preparation described below and squeezed off toa liquor pickup of 100%.

    ______________________________________                                         50 parts of the dye according to Example 1                                    300 parts of urea                                                             320 parts of Solvitose OFA ® at 40% (thickener)                           10 parts of a mixture of anion-active fatty alcohol ether sulfate               with non-ionic wetting agents                                               10 parts of the levelling agent used in Dyeing Example 1                      10 parts of sodium metabisulfite                                              10 parts of 80% acetic acid                                                   290 parts of water                                                           1000 parts of padding liquor                                                  ______________________________________                                    

The impregnated fabric is then stored at room temperature for 48 hourswhile rolled-up and wrapped air-tight. After rinsing with cold water,the material is treated in a fresh bath with such an amount of 24%ammonia that a pH of 8.5 is obtained and maintained at 80° for 15minutes. After rinsing in warm water, it is finally acidified with 80%acetic acid and dried. The wool fabric has been dyed in a full blueshade which has excellent fastness properties.

DYEING EXAMPLE 4

A flannel fabric consisting of chlorinated wool is impregnated on apad-mangle with the dye preparation described below and squeezed off toa liquor pickup of 100%.

    ______________________________________                                         50 parts of the dye according to Example 1                                    300 parts of Solvitose OFA ® at 40% (thickener)                           20 parts of a mixture of anion-active fatty alcohol ether sulfate               with non-ionic wetting agents                                               10 parts of the levelling agent used in Dyeing Example 1                      20 parts of 80% acetic acid                                                   600 parts of water                                                           1000 parts of padding liquor                                                  ______________________________________                                    

The impregnated fabric is then taken to a steaming cabinet and treatedwith saturated steam for 20 to 40 minutes. After rinsing with coldwater, the material is treated in a fresh bath with such an amount of24% ammonia that a pH of 8.5 is obtained and maintained at 80° for 15minutes. After rinsing in warm water, it is finally acidified with 80%acetic acid and dried. The wool fabric has been dyed in a full blueshade which has excellent fastness properties.

DYEING EXAMPLE 5

4 parts of 80% acetic acid, 2 parts of the ammonium salt of themonosulfate of the adduct of a fatty amine (consisting of 30% ofhexadecylamine, 25% of octadecylamine and 45% of octadecenylamine and 7mol of ethylene oxide) and 4 parts of ammonium sulfate are dissolved insuccession in 1000 parts of water at 50°.

3 parts of the dye obtained according to Example 1 are dissolved in 100parts of hot water and added to the above dyebath. A circulation dyeingapparatus is charged with 100 parts of prewetted tops in the form ofwound packages, and the temperature of the bath is increased from 50° to97°-99° over a period of 30 minutes, and the material is then dyed for90 minutes at the boiling temperature. The dye shows almost completeexhaustion onto the substrate. After the bath has been cooled to 80°,the pH of about 4.5 is raised to a permanent value of 8.5 by addingammonia solution, and the dyed material is aftertreated at thistemperature for 20 minutes. After thorough rinsing with hot and coldwater, acidification with 1 part of 80% formic acid, centrifugation anddrying, a dark blue coloured material of very good wet fastness andexcellent light fastness is obtained.

DYEING EXAMPLE 6

6 parts of 80% acetic acid, 3 parts of the ammonium salt of themonosulfate of the adduct of a fatty amine (consisting of 30% ofhexadecylamine, 25% of octadecylamine and 45% of octadecenylamine and 7mol of ethylene oxide) and 6 parts of ammonium sulfate are dissolved insuccession in 1000 parts of water at 50°.

3 parts of the dye obtained according to Example 1 are dissolved in 100parts of hot water and added to the above dyebath. A circulation dyeingapparatus is charged with 150 parts of prewetted loose wool, and thetemperature of the liquor is increased from 50° to 97°-99° over a periodof 30 minutes, and the material is then dyed for 90 minutes at theboiling temperature. The dye shows almost complete exhaustion onto thesubstrate. After the bath has been cooled to 80°, the pH of about 4.5 israised to a permanent value of 8.5 by adding ammonia solution, and thedyed material is aftertreated at this temperature for 20 minutes. Afterthorough rinsing with hot and cold water, acidification with 1 part of80% formic acid, centrifugation and drying, a substrate dyed in a bluelevel shade of very good wet and rub fastness and excellent lightfastness is obtained.

DYEING EXAMPLE 7

4 parts of 80% acetic acid, 2 parts of the ammonium salt of themonosulfate of the adduct of a fatty amine (consisting of 30% ofhexadecylamine, 25% of octadecylamine and 45% of octadecenylamine and 7mol of ethylene oxide) and 4 parts of ammonium sulfate are dissolved insuccession in 4000 parts of water at 50°.

0.45 part of the dye obtained according to Example 1 and 0.30 part ofthe yellow dye of the formula ##STR18## and 0.40 part of the red dye ofthe formula ##STR19## are dissolved in 100 parts of hot water and addedto the above dyebath. 100 parts of a prewetted wool fabric are thenplaced into the dyebath, and the temperature of the bath is increasedfrom 50° to 80° over a period of 30 minutes. After dyeing at 80° for 20minutes, the bath is heated to boiling, and dyeing is then continued for90 minutes at the boiling temperature. The dye shows almost completeexhaustion onto the substrate. After the bath has been cooled to 80°,the pH of about 4.5 is raised to a permanent value of 8.5 by addingammonia solution, and the dyed material is aftertreated at thistemperature for 20 minutes. After thorough rinsing with hot and coldwater, acidification with 1 part of 80% formic acid, centrifugation anddrying, a wool fabric dyed in a level dark brown shade of very good wetand rub fastness and excellent light fastness is obtained.

DYEING EXAMPLE 8

4 parts of 80% acetic acid, 2 parts of the ammonium salt of themonosulfate of the adduct of a fatty amine (consisting of 30% ofhexadecylamine, 25% of octadecylamine and 45% of octadecenylamine and 7mol of ethylene oxide) and 4 parts of ammonium sulfate are dissolved insuccession in 4000 parts of water at 50°.

0.6 part of the dye obtained according to Example 2 and 0.09 part of theyellow dye of the formula ##STR20## and 0.2 part of the red dye of theformula ##STR21## are dissolved in 100 parts of hot water and added tothe above dyebath. A circulation dyeing apparatus is charged with 100parts of prewetted tops in the form of wound packages, and thetemperature of the bath is increased from 50° to 97°-99° over a periodof 30 minutes, and the material is then dyed for 90 minutes at theboiling temperature. The dye shows almost complete exhaustion onto thesubstrate. After the bath has been cooled to 80°, the pH of about 4.5 israised to a permanent value of 8.5 by adding ammonia solution, and thedyed material is aftertreated at this temperature for 20 minutes. Afterthorough rinsing with hot and cold water, acidification with 1 part of80% formic acid, centrifugation and drying, a grey coloured material ofvery good wet and rub fastness and excellent light fastness is obtained.

What is claimed is:
 1. A trichromic dye mixture, which contains afibre-reactive formazan dye of the formula ##STR22## in which R is C₁-C₄ alkyl, C₁ -C₄ alkoxy, halogen, cyano or nitro, X is fluorine orchlorine, and n is the number 0, 1 or 2 together with a fibre-reactivesulfo-containing yellow or orange dye of the formula ##STR23## andtogether with a sulfo-containing fibre-reactive red dye of the formula##STR24## whereby in the formulae above acyl is acetyl or benzoyl, thefused rings indicated by dots represent naphthalene systems which arepossible as an alternative and R' is difluorochloropyrimidinyl orα,β-dihalogenopropionyl or α-halogenoacryloyl.